Forming Substrate Structure by Filling Recesses with Deposition Material

ABSTRACT

A substrate structure is produced by forming a first material layer on a substrate having a recess, removing the first material layer from the portion of the substrate except for the recess using a second material that reacts with the first material, and forming a deposition film from the first material layer using a third material that reacts with the first material. A method of manufacturing a device may include the method of forming a substrate structure.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) to co-pendingU.S. Provisional Patent Application No. 61/088,679 entitled “Method ofForming Substrate Structure and Method of Manufacturing DeviceComprising the Same” filed on Aug. 13, 2008, which is incorporated byreference herein in its entirety.

BACKGROUND

1. Field of Art

This invention relates to forming a substrate structure with depositionmaterial filling one or more recesses on a substrate.

2. Description of Related Art

Many semiconductor devices include transistors, wirings, insulators andother components formed on a substrate. Conventionally, transistors areinsulated from each other using technique such as LOCOS (local oxidationof silicon) or SEPOX (selective poly oxidation). To accommodatesemiconductor devices with smaller components for higher level ofintegration, a technique called STI (Shallow Trench Isolation) wasdeveloped. The STI forms trenches around the periphery of a transistorand then fills the trenches with silicon oxide (SiO₂). In order to fillthe trenches with SiO₂, techniques such as atmospheric pressure chemicalvapor deposition (APCVD), high density plasma (HDP) oxide deposition,and sub-atmospheric chemical vapor deposition (SACVD) are be used. Theseconventional techniques, however, are not suitable to fill the trenchesin cases where 45 nm or smaller design rules apply, or an aspect ratioof 5:1 or larger applies.

FIG. 1A is a schematic diagram illustrating a substrate 1 with a recess2 filled using a conventional technique. In FIG. 1A, the recess 2 may befilled with O₃-TEOS oxide 3 by SACVD using tetraethyl orthosilicate(TEOS) as a source precursor and using ozone as a reaction precursor.However, the recess 2 may not be filled completely, if the width (orpitch) of the recess 2 is small or the aspect ratio is high.Consequently, voids 4 are formed in the recess, which reduces thereliability of the semiconductor device.

FIG. 1B is a schematic diagram illustrating the substrate 1 with therecess 2 using a conventional technique. FIG. 1B illustrates the recess2 on the substrate 1 filled using an HDP apparatus implementing chemicalvapor deposition (CVD) while controlling the bias of the substrate toetch the substrate. The conventional technique of FIG. 1B reducesoverhang of the oxide 5 deposited at the edge of the recess 2 byresputtering. However, the HDP oxide 5 accumulates at the bottom of therecess 2. Hence, this convention technique may cause damage to thesubstrate 1 by bias or plasma. Further, if the aspect ratio of therecess 2 is high, then the recess 2 may be filled partially, resultingin uneven coating of the substrate 1.

SUMMARY

Embodiments provide a method for forming a substrate structure with oneor more recesses filled with a dielectric material, a semiconductormaterial or metal to provide wirings having advantageous electrical andmechanical properties. A first material layer may be formed on asubstrate having one or more recesses. The first material layer may thenbe removed from portions of the substrate other than surfaces of therecesses by using a second material that reacts with the first material.A deposition film is formed from the first material layer remaining inthe recesses using a third material that reacts with the first material.

Embodiments also provide a method of manufacturing a device including asubstrate structure formed using such method.

In another embodiment, a substrate structure may be fabricated byforming a deposition film on a substrate having one or more recesses,and removing the deposition film from the substrate other than thesurfaces of the recesses using a first material that reacts with thedeposition film.

In one embodiment, the deposition film is formed in the one or morerecesses on the substrate to fill the interior of the recess withmaterials such as a dielectric material, a semiconductor material andmetal.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A and FIG. 1B are schematic diagrams illustrating a recess on asubstrate filled.

FIG. 2A through FIG. 2I are schematic diagrams illustrating a process offorming a substrate structure, according to an embodiment.

FIG. 3A through FIG. 3I are schematic diagrams illustrating a process offorming a substrate structure, according to another embodiment.

FIG. 4A and FIG. 4B are schematic diagrams illustrating a process offorming a substrate structure, according to still another embodiment.

FIG. 5A through FIG. 5C are schematic diagrams illustrating the portionof a recess of a substrate in which a deposition film is formeddepending on the incident angle of UV (Ultraviolet) light, according toan embodiment.

FIG. 6 is a schematic diagram illustrating the surface of a substrateOH-treated in a process of forming a substrate structure according to anembodiment.

DETAILED DESCRIPTION OF EMBODIMENTS

Hereinafter, reference will now be made in detail to various exampleembodiments, examples of which are illustrated in the accompanyingdrawings and described below. While the invention will be described inconjunction with example embodiments, it will be understood that thepresent description is not intended to limit the invention to thoseexample embodiments. On the contrary, the invention is intended to covernot only the example embodiments, but also various alternatives,modifications, equivalents and other embodiments, which may be includedwithin the spirit and scope of the invention as defined in the appendedclaims. In the following, description of known functions orconstructions which may unnecessarily obscure the subject matter of thepresent invention will be omitted.

The number and types of atoms or molecules constituting each materialare provided in Figures for the purpose of illustration. The presentinvention is not limited by the number and types of atoms or moleculesconstituting each material. For example, each material may have a numberof molecules different from Figures, and each molecule may have numberand types of atoms different from Figures.

FIG. 2A through FIG. 2I are schematic diagrams illustrating a process offorming a substrate structure, according to one embodiment. First,referring to FIG. 2A, a substrate 1 having a recess 2 is prepared. Thenumber, depth, width and shape of the recess 2 illustrated in the FIGS.2A through 2I are provided merely for the purpose of illustration. Inother embodiments, the number, depth, width and shape of the recess maydiffer.

Referring next to FIG. 2B and FIG. 2C, a layer of a first material 10 isformed on the substrate 1 having the recess 2. In one embodiment, thefirst material 10 is a source precursor for forming a deposition film.Referring to FIG. 2B, the layer of the first material 10 may be formedby exposing the substrate 1 to the first material 10. For example, thesubstrate 1 may be sprayed with the first material 10. The firstmaterial 10 may be sprayed on the substrate 1 in such an amount that thefirst material 10 is adsorbed chemically and physically on the entiresurface of the substrate 1 to saturate the surface of the substrate 1.

In one embodiment, the layer of the first material 10 is formed on theentire surface of the substrate 1 using a showerhead type spray nozzlethat exposes the entire surface of the substrate to the first material10 simultaneously. The layer of the first material may also be formedthrough atomic layer deposition similar to ejection through theshowerhead type spray nozzle. For example, a deposition apparatus havinga nozzle for ejecting the first material 10 placed above the substrate 1is used. Alternatively, the first material 10 may be ejected on theentire surface of the substrate 1 by transferring the substrate 1 whileejecting the file material 1 on a portion of the substrate 1.

In one embodiment, the substrate 1 is exposed to a radical generatingapparatus, remote plasma, microwave, electron cyclotron resonance plasmaor ultraviolet (UV) light so that the substrate 1 absorbs the firstmaterial 10. It may be difficult to have some silicon-containingcompounds chemisorbed on the substrate 1. In such case, the substrate 1may absorb the silicon-containing compounds by using radicals or thelike, as described above in detail. Further, in one embodiment, acatalyst may be ejected onto the substrate 1.

In one embodiment, when forming a deposition film of a dielectricmaterial in the recess 2, the first material 10 may be a silicon (Si) oraluminum (Al) containing material. For instance, the first material 10may be an inorganic silicon compound such as a silicon hydride compoundor a silicon chloride compound. The first material 10 may comprise atleast one of SiH₄, SiCl₄, Si₂H₆, Si₂Cl₆, SiH₂Cl₂ and Si₃H₈.

Alternatively, the first material 10 may be a silicon or aluminumcontaining organic compound such as an alkyl compound, an alkanecompound or an amine compound. For example, the first material 10 may bean alkyl compound having an Si—H bond, such as monomethylsilane (MMS;CH₃SiH₃), dimethylsilane (DMS; (CH₃)₂SiH₂), trimethylsilane (TMS;(CH₃)₃SiH), monoethylsilane (C₂H₅SiH₃), diethylsilane ((C₂H₅)₂SiH₂),triethylsilane ((C₂H₅)₃SiH) and 1,3-disilabutane (CH₃CH₂SiH₂SiH₃).

Alternatively, the first material 10 may be an alkoxide compound havingan Si—H bond, such as trimethoxysilane (SiH(OCH₃)₃) or triethoxysilane(SiH(OC₂H₅)₃). Further, the first material 10 may be a siloxane compoundhaving an Si—H bond, such as tetramethyldisiloxane (TMDSO;(CH₃)₂HSi—O—SiH(CH₃)₂).

Further, the first material 10 may be a silicon-containing aminecompound, such as hexamethyldisilazane (HMDS; (CH₃)₃Si—NH—Si(CH₃)₃) or acompound modified therefrom.

Still further, the first material 10 may be an aluminum-containing alkylcompound, such as trimethylaluminum (TMA; Al(CH₃)₃), dimethylaluminumhydride (DMAH; Al(CH₃)₂H)), dimethylaluminum isopropoxide (DMAIP;(CH₃)₂AlOCH(CH₃)₂)) or a compound modified therefrom.

Further, the first material 10 may be an aluminum-containing aminecompound, such as dimethylethylaminoaluminum (DMEAA; AlH₃N(CH₃)₂(C₂H₅))or a compound modified therefrom.

In another embodiment, a deposition film of a semiconductor material maybe formed in the recess 2. In this case, the first material 10 may be asilicon-containing inorganic compound, a germanium (Ge)-containinginorganic compound, or a carbon compound. For example, the firstmaterial 10 may be a silicon or germanium containing hydrogen compoundor a silicon or germanium containing chlorine compound comprising atleast one of SiH₄, SiCl₄, Si₂H₆, Si₂Cl₆, SiH₂Cl₂, Si₃H₈, GeH₄, GeCl₄,Ge₂H₆, Ge₂Cl₆, GeH₂Cl₂ and Ge₃H₈.

Alternatively, when forming carbon-doped silicon in the recess 2, thefirst material 10 may be a carbon compound, including an alkane compoundsuch as CH₄, C₂H₆ and C₃H₈, or an alkyl compound such as (CH₃)SiH₃,(CH₃)GeH₃, (C₂H₅)SiH₃ and (C₂H₅)GeH₃.

Further, when forming an oxide semiconductor such as ZnO, NiO, CeO orEuO in the recess 2, the first material 10 may be an alkyl compound or acompound modified therefrom.

Still further, when forming a nitride semiconductor such as AlN, GaN orInN in the recess 2, the first material 10 may be an alkyl compound,such as dimethylaluminum hydride, trimethylaluminum, triethylaluminum,trimethylgallium (TMG; Ga(CH₃)₃), trimethylgallium (TEG; Ga(C₂H₅)₃),trimethylindium (TMI; In(CH₃)₃), trimethylindium (TEI; In(C₂H₅)₃)) or acompound modified therefrom. Also, in this case, the first material 10may be an amine compound, such as dimethylethylaminealuminum,dimethylaminobutylaluminum and a compound modified therefrom.

In still another example embodiment, a deposition film of a metalmaterial, a high melting point compound or a metal-silicon compound maybe formed in the recess 2. In this case, the first material 10 maycomprise at least one of an inorganic metal compound, an alkyl compoundand a compound modified therefrom. For example, the first material 10 isan inorganic metal compound such as AlCl₃, TiCl₄, TaCl₅, WF₆, etc, analkyl compound such as trimethylaluminum, triethylaluminum,dimethylaluminum hydride and a compound modified therefrom.

Referring next to FIG. 2C, the first material except for the firstmaterial layer 10 that is chemisorbed on the substrate 1 may be removedby ejecting a purge gas onto the substrate and pumping out the purgegas. The purge gas may be an inert gas such as argon (Ar). The bondingstrength of the chemisorption tends to be stronger than physisorption.Accordingly, it is possible to remove, through the purge gas, thephysisorbed molecules while retaining only the chemisorbed layer of thefirst material 10 on the substrate 1.

Referring next to FIG. 2D and FIG. 2E, the first material layer 10 isremoved from the portion of the substrate 1 other than the surfaces ofthe recess 2, using a second material 20. Referring to FIG. 2D, thesubstrate 1 on which the first material layer 10 is formed may beexposed to the second material 20. The duration for exposing thesubstrate 1 to the second material 20 may be controlled such that thesecond material 20 does not diffuse into the recess 2 of the substrate1. To this end, the duration for exposing the substrate 1 to the secondmaterial 20 may be controlled to prevent the second material 20 fromentering the recess 2. An injector (not illustrated) separated from thesubstrate 1 may eject the second material 20 onto the substrate 1.

The second material 20 may be ejected with a predetermined speed. Thetime required for the second material 20 to reach the substrate 1 may becalculated from (i) the distance between the substrate 1 and theinjector, and (ii) the ejection speed of the second material 20. Theduration for ejecting the second material 20 is controlled so that theejection is stopped as soon as the second material 20 reaches thesubstrate 1. In this way, diffusing of the second material 20 into therecess 2 of the substrate 1 may be prevented.

The duration for ejecting the second material 20 onto the substrate 1may be controlled to provide an extremely short burst of the secondmaterial. Hence, an injector or a showerhead with a superior uniformitymay be used to inject the second material 20 onto the substrate 1. Thesubstrate 1 may be fixed by a variable susceptor that controls thedistance between the injection outlet of the second material 20 and thesubstrate 1.

In another embodiment, a scanning type deposition apparatus is used todeposit the second material 20. The scanning type deposition apparatusdeposits the second material 20 onto the substrate 1 by moving thesubstrate 1 while exposing the substrate 1 to the second material 20.For instance, the substrate 1 is placed on a conveyer (not illustrated)and moved at a controlled speed in a region where the substrate 1 isexposed to the second material 20. By controlling the speed of theconveyor, it is possible to prevent the second material 20 from enteringthe recess 2. That is, the substrate 1 is exposed to the second material20 and then transferred by the conveyer out of the region before thesecond material 20 diffuses into the recess 2 of the substrate 1.Besides preventing the second material 20 from diffusing into the recess2, moving the substrate 1 via the conveyor is advantageous because theoverall productivity (throughput) of producing the substrate 1 may beincreased by increasing the transfer rate of the substrate 1.

In still another embodiment, when using radicals such as hydrogenradicals produced from remote plasma as the second material 20, thedistance between the remote plasma and the substrate 1 may be controlledsuch that the second material 20 is not diffused into the recess 2.Radicals have relatively short lifetime. Hence, by positioning thesubstrate 1 so that the time required for the radicals to reach thesubstrate 1 is equal to or approximate the lifetime of the radicals, itis possible to prevent the radicals from diffusing into the recess 2.The plasma used for this purpose may be parallel plate plasma producedin parallel to the substrate, inductive coupled plasma produced using acoil, many arc plasma in which a plurality of plasma arcs are producedin parallel to the substrate, or the like.

Further, in one embodiment, when the second material 20 is activated byUV (Ultraviolet) light to react with the first material 10, it ispossible to control the incident angle of UV light such that the secondmaterial 20 does not react with the first material 10 in the recess 2,as described below in detail with reference to FIG. 5.

The above descriptions are given for the purpose of illustration only.In other embodiments, it is possible prevent the first material 10 fromreacting with the second material 20 in the recess 2 of the substrate 1in a different manner. As a result, the second material 20 may reactwith the first material layer 10 on the portion 100 of the substrate 1other than the surfaces of the recess 2.

By reacting with the first material 10, the second material 20 mayremove the first material layer 10 from the substrate 1. For thispurpose, the second material 20 may be a reactive gas capable ofreacting with the first material 10 to form a volatile material.

In one embodiment, the second material 20 comprises at least one ofhydrogen, chlorine, fluorine and radicals thereof. For example, thesecond material 20 may comprise at least one of HCl, BCl₃, ClF₃ and NF₃.

In one embodiment, the substrate 1 is exposed to remote plasma, aradical generation apparatus, microwave, electron cyclotron resonanceplasma or UV light depending on the second material such that the firstmaterial 10 reacts with the second material 20. In this case, theincident angle of UV light may be controlled such that the secondmaterial 20 does not react with the first material 10 in the recess 2,as described below in detail with reference to FIG. 5.

Referring to FIG. 2E, in one embodiment, purging may be carried outafter the second material 20 reacts with the first material 10. By usingthe purge gas, the volatile material produced as a result of thereaction between the second material 20 and the first material 10, andthe second material 20 remaining after the reaction may be removed. Thisprocess removes the first material layer 10 from the portion 100 of thesubstrate 1 other than the surfaces of the recess 2, leaving behind onlythe first material 10 absorbed in the surface 200 of the recess 2.

Referring next to FIG. 2F and FIG. 2G, a deposition film 40 may beformed in the recess 2 based on the first material layer 10. Referringto FIG. 2F, a third material 30 is exposed to the substrate 1 where thefirst material layer 10 is formed in the recess 2. The third material 30may react with the first material layer 10 to form the deposition film40 in the recess 2. That is, the third material 30 may be a reactionprecursor for forming the deposition film 40.

In one embodiment, a deposition film 40 comprising a dielectric materialsuch as oxide or nitride may be formed depending on the first materiallayer 10. For instance, the deposition film 40 comprises at least one ofSiO₂, PSG, BPSG, SiN, Al₂O₃ and AlN.

If the deposition film 40 comprises an oxide, the third material 30 maycomprise at least one of H₂O, H₂O plasma, O₂, O₂ plasma, N₂O, N₂O plasmaand O₃. If the deposition film 40 comprises a nitride, the thirdmaterial 30 may comprise at least one of NH₃, NH₃ plasma and N₂ plasma.

In one embodiment, a deposition film 40 comprising a semiconductormaterial is formed depending on the first material layer 10. Forinstance, the deposition film 40 comprises Si, Ge,Si_(x)Ge_(1−x)(0<x<0.5), boron-doped Si, phosphorus-doped Si orcarbon-doped Si. Further, the deposition film 40 is formed of an oxidesemiconductor such as ZnO, NiO, CeO, and EuO or a nitride semiconductorsuch as AlN, GaN, and InN. In this case, the third material 30 maycomprise at least one of nitrogen radical, NH₃ plasma and N₂ plasma.

In one embodiment, the deposition film 40 is formed of a metal material,a high melting point compound or a metal-silicon compound. For instance,deposition film 40 includes at least one of a metal material such as Al,Ti, Ta, W, and Cu; a high melting point compound such as TiN, TaN, andWN metal compound such as GeSbTe, CuInGaSe; or a metal-silicon compoundcompound such as NiSi, CoSi, and TiSi.

Referring next to FIG. 2G, excess third material 30 is removed bypurging after the reaction, as described above in detail with referenceto FIG. 2C. As a consequence, the deposition film 40 is formed in therecess 2 of the substrate 1. In FIG. 2G, the deposition film 40 isdepicted as consisting of two different atoms. This is onlyillustrative. The deposition film 40 may consist of a single atom ormore than three different atoms.

As illustrated in FIG. 2H, multiple layers of the deposition film 40 areformed in the recess 2 of the substrate 1 by repeating the processes,described above in detail with reference to FIG. 2B through FIG. 2G. Asillustrated in FIG. 2I, the recess 2 of the substrate 1 may becompletely filled with the deposition film 40 by repeating theprocesses, described above in detail with reference to FIG. 2B throughFIG. 2G.

FIG. 3A through FIG. 3I are schematic diagrams illustrating a method offorming a substrate structure, according to another embodiment.Referring to FIG. 3A, a substrate 1 having a recess 2 is prepared. Thenumber, depth, width and shape of the recess illustrated in the Figuresare merely for the purpose of illustration, and they may be varied.

Referring next to FIG. 3B and FIG. 3C, a deposition film 50 is formed onthe substrate 1 having the recess 2. In one embodiment, the depositionfilm 50 is formed by atomic layer deposition to expose the substrate 1to a source precursor 51 and a reaction precursor (not illustrated). Thesubstrate 1 may be exposed simultaneously to the source precursor 51 andthe reaction precursor.

In one embodiment, the deposition film 50 is an atomic layer comprisingsilicon, aluminum or titanium. In this case, the deposition film 50 maybe formed by plasma-enhanced atomic layer deposition to deposit a sourcematerial onto the substrate 1 using plasma.

The deposition film 50 may be a silicon atomic layer. In this case, thedeposition film 50 comprising silicon may be formed by exposing thesubstrate 1 to the source precursor 51 and the reaction precursor. Thesource precursor 51 may comprise a silicon-containing inorganic compoundsuch as a silicon hydride compound or a silicon chloride compound; or asilicon-containing organic compound such as an alkyl compound, an alkanecompound or an amine compound.

Alternatively, the deposition film 50 may be an aluminum atomic layer.In this case, the source precursor 51 may be an aluminum-containingorganic compound.

Alternatively, the deposition film 50 is a titanium (Ti) atomic layer.In this case, the source precursor 51 may comprise, for example, TiCl₄.

The deposition film 50 may be formed by reaction between the sourceprecursor 51 and the reaction precursor. In this embodiment, thereaction precursor comprises hydrogen plasma.

Referring next to FIG. 3C, a purge method is performed to remove excessreaction precursor and source precursor and to form the atomic layertype deposition film 50 on the substrate 1.

Referring next to FIG. 3D and FIG. 3E, the deposition film 50 may beremoved from the portion of the substrate 1 other than the surfaces ofthe recess 2 using a first material 60. Referring to FIG. 3D, thesubstrate 1 with the first deposition film 50 is exposed to the firstmaterial 60. The duration for exposing the substrate 1 to the firstmaterial 60 may be controlled such that the first material 60 does notdiffuse into the recess 2 of the substrate 1. Example ways of preventingthe first material 60 from entering the recess 2 are described above indetail with reference to FIG. 2D.

The first material 60 may react with the deposition film 50 formed onthe substrate 1 to remove the deposition film 50 from the substrate 1.For this purpose, the first material 60 may be a reactive gas thatreacts with the deposition film 50 to form a volatile material.

In one embodiment, the first material 60 comprises at least one ofhydrogen, chlorine, fluorine and radicals thereof. For example, thefirst material 60 comprises at least one of HCl, BCl₃, ClF₃ and NF₃.

In one embodiment, the substrate 1 is exposed to remote plasma, aradical generation apparatus, microwave, electron cyclotron resonanceplasma or UV light, depending on what the first material 60 is, suchthat the deposition film 50 may be removed from the substrate 1.

In one embodiment, when the first material 60 is activated by UV lightto react with the deposition film 50, it is possible to control theincident angle of UV light such that the first material 60 does notreact with the deposition film 50 in the recess 2, as described below indetail with reference to FIG. 5.

Referring to FIG. 3E, one embodiment is illustrated where purging isperformed using, for example, an inert gas after the first material 60reacts with the deposition film 50. By using the purge method, thevolatile material produced from the reaction of the first material 60and the deposition film 50, and excess first material 60 may be removed.As a consequence, the deposition film 50 may be removed from the portion100 of the substrate 1 other than the surfaces of the recess 2, leavingbehind only the deposition film 50 on the surface 200 of the recess 2.

Referring to FIG. 3F and FIG. 3G, in one embodiment, the deposition film50 formed on the portion of the substrate 1 other than the surfaces ofthe recess 2 reacts with a second material 70 to form a modified film80. Referring to FIG. 3F, the substrate 1 with the deposition film 50 inthe recess 2 may be exposed to the second material 70. The secondmaterial 70 reacts with the deposition film 50 to form the modified film80 in the recess 2. That is, the second material 70 may be a reactionprecursor for forming the modified film 80.

In one embodiment, the modified film 80 comprises an oxide or a nitride.For example, if the modified film 80 comprises an oxide, the secondmaterial 70 comprises at least one of H₂O, H₂O plasma, O₂, O₂ plasma,N₂O, N₂O plasma and O₃. If the modified film 80 comprises a nitride, thesecond material 70 comprises at least one of NH₃, NH₃ plasma, N₂ plasmaand nitrogen radical. In this case, the modified film 80 may be formedof an oxide or a nitride, depending on the deposition film 50 and thesecond material 70. For instance, the modified film 80 may comprise atleast one of SiO₂, SiN, Al₂O₃, AlN, TiO₂ and TiN.

Referring next to FIG. 3G, excess second material 70 is removed bypurging gas, as described above. As a consequence, the modified film 80comprising a nitrogen or oxygen compound may be formed in the recess 2of the substrate 1. In FIG. 3G, the modified film 80 is illustrated asconsisting of two different atoms. This is merely illustrative. Themodified film 80 may consist of a single atom or more than threedifferent atoms.

Referring to FIG. 3H, multiple layers of the modified film 80 are formedin the recess 2 of the substrate 1 by repeating the processes describedwith reference to FIG. 3B through FIG. 3G. The recess 2 of the substrate1 may be completely filled with the modified film 80 by repeating theprocesses several times, as illustrated in FIG. 3I. Further, if theprocesses of modification by the second material is not performed, therecess 2 may be filled with the atomic layer type deposition film 50 inFIG. 3E.

FIG. 4A and FIG. 4B are schematic diagrams illustrating the process offorming a substrate structure according to still another embodiment.Referring to FIG. 4A, a deposition film 40 is formed in recesses 2 of asubstrate 1 according to processes of forming a substrate structure, asdescribed above in detail with reference to FIG. 2A through FIG. 3I. Bycontrolling the degree of diffusion of a reactive gas or other materialinto the recesses 2, or the reaction level in the recesses 2, thedeposition film 40 is not formed over a predetermined depth D in therecesses 2, as illustrated in FIG. 4A. Accordingly, the recess 2 may isnot filled completely with the deposition film 40.

Referring to FIG. 4B, an additional deposition film 45 may be formedover the entire surface of the substrate 1 having the partly-filledrecesses 2. By depositing the deposition film 40 and the deposition film45, each of which partly fill the recesses, the entire surface of thesubstrate 1 and the recess 2 may be filled completely, without anyuneven covering.

FIG. 5A through FIG. 5C are schematic diagrams illustrating portions ofrecesses of a substrate filled by exposing the substrate 1 and therecesses 2 to UV light, according to one embodiment. The recesses 2 maybe partially filled by partly removing material from the portion of asubstrate 1 other than the surfaces of the recesses 2 using, forexample, a reactive gas. When a reactive gas activated by UV light isused, the incident angle of UV light to the substrate 1 may becontrolled so that the material is selectively removed from thesubstrate 1 other than the surfaces of the recess 2. Referring to FIG.5A, the UV light is incident with a predetermined incident angle θ tothe substrate 1. If the incident angle θ of UV light is sufficientlylarge, UV light may reach the bottom of the recess 2. If the incidentangle θ is smaller, however, UV light will reach only a portion of therecess 2.

Referring to FIG. 5B, if the incident angle θ is sufficiently small andUV light reaches a predetermined depth D of the recesses 2, the reactivegas may be activated in the recesses 2 above the depth D and thematerial deposited in the recess 22 may be removed. As a result, therecesses 2 are filled partly. Accordingly, referring to FIG. 5C, if theincident angle θ of UV light is sufficiently small, the reactive gas maynot be activated inside the recesses 2, and the recesses 2 may becompletely filled with a deposition film 40.

FIG. 6 is a schematic view illustrating the surface of a substrate thatis OH-treated, according to one embodiment. In this embodiment, theprocess of treating the surface of the substrate with OH bonds may beperformed before performing the process of forming a substratestructure, as described above in detail with reference to FIG. 2Athrough FIG. 3I.

In order to form a substrate structure by atomic layer deposition, itmay be advantageous to use a material that is effectively chemisorbed inthe substrate as precursor. However, some materials used in CVD such asTEOS, do not have ligands or bonds required for selective chemisorption.

To ensure chemisorption of the precursor, the surface of the substrate 1must be sufficiently terminated with OH. Accordingly, in one embodiment,a separate termination process must be performed on the surface of thesubstrate 1 before carrying out the process of forming the substratestructure, as described above in detail with reference to FIG. 2Athrough and FIG. 3I. Even when H₂O is injected from a chamber,adsorption may not occur sufficiently because the surface of thesubstrate cleaned by HF solution may not be hydrogen-terminated. Thismay cause the so-called incubation phenomenon and may require a numberof additional adsorption processes for absorption of H₂O. Therefore, inthis embodiment, the process of exposing the substrate to H₂O plasma orremote plasma in order to produce hydroxyl radicals ((OH)*) may also beperformed.

A direct application of H₂O plasma to the substrate 1 may negativelyaffect the substrate 1 itself or a device mounted on the substrate 1.Accordingly, in one embodiment, plasma may be generated at a locationaway from the substrate 1 using H₂O gas produced by forming Ar bubblesin deionized water (DI water). The substrate 1 may be exposed to theradicals produced by generating the plasma remote from the plasma.

In another embodiment, radicals produced by plasma may be injected intoan H₂O injector to produce hydroxyl radicals ((OH)*). Hydroxyl radicals((OH)*) are provided to the substrate 1. Alternatively, an electrode maybe installed perpendicular to the substrate 1. The plasma may then begenerated in parallel to the substrate so that radicals may contact thesubstrate 1.

The substrate 1 treated by oxygen-supplying materials may have OH bonds,as illustrated in FIG. 6. That is, the substrate 1 may have ahydrophilic surface. Accordingly, when a material is provided on theOH-treated substrate, chemisorption may occur on the surface of thesubstrate 1 as the OH bonds are substituted by the material.

The above embodiments are described with reference to atomic layerdeposition. This is, however, merely illustrative. In other embodiments,a deposition film may be formed in a recess of a substrate, for example,by chemical vapor deposition.

The substrate structure formed according to embodiments may be utilizedto form materials such as oxide and nitride in the recess of asubstrate. Further, the recess may be filled completely by repeating theprocesses. Accordingly, recesses in STI, contact holes, via holes ofmultiplayer wirings and through-silicon via (TSV) or the like with alarge aspect ratio may be filled at low temperature.

Further, the process of forming a substrate structure according toembodiments may be utilized to form a semiconductor or metal material inthe recess. Accordingly, a substrate structure may be used to fill thecontact hole, via hole for multilayer wirings, or through-silicon via(TSV) for 3-dimensional packaging.

Further, it is possible to partially fill the recess because the depthat which the deposition film is formed in the recess may be adjusted bycontrolling the ejection speed or time of reactive gas, the transferrate of the substrate or the like. Therefore, step coverage may becontrolled as desired.

Although the present invention has been described above with respect toseveral embodiments, various modifications can be made within the scopeof the present invention. Accordingly, the disclosure of the presentinvention is intended to be illustrative, but not limiting, of the scopeof the invention, which is set forth in the following claims.

1. A method for forming a substrate structure, comprising: forming afirst material layer on a substrate, one or more recesses formed on thesubstrate; removing the first material layer from the substrate otherthan surfaces of the one or more recesses using a second material thatreacts with the first material layer; and forming a deposition film fromthe first material layer using a third material that reacts with thefirst material layer.
 2. The method of claim 1, wherein removing thefirst material layer comprises controlling duration during which thesubstrate is exposed to the second material so that the surfaces of theone or more recesses are not exposed to the second material.
 3. Themethod of claim 1, further comprising: exposing the substrate to a purgegas responsive to forming the first material layer, removing the firstmaterial layer or forming the deposition film; and pumping out the purgegas.
 4. The method of claim 1, wherein the first material layer is asource precursor and the third material is a reaction precursor.
 5. Themethod of claim 1, wherein the deposition film is formed of a dielectricmaterial.
 6. The method of claim 1, wherein the deposition filmcomprises at least one of an oxide or a nitride.
 7. The method of claim1, wherein the deposition film comprises at least one of SiO₂, PSG,BPSG, Al₂O₃, TiO₂, HfO₂, ZrO₂, ZnO, NiO, SiN and AlN.
 8. The method ofclaim 1, wherein the first material layer comprises a silicon-containinginorganic compound or aluminum.
 9. The method of claim 1, wherein thefirst material layer comprises at least one of SiH4, SiCl4, Si2H6,Si2Cl6, SiH2Cl2, Si3H8, an alkyl compound having an Si—H bond, analkoxide compound having an Si—H bond, a siloxane compound having anSi—H bond, a silicon-containing amine compound, or a compound modifiedtherefrom.
 10. The method of claim 1, wherein the first material layercomprises an aluminum-containing alkyl compound, an aluminum-containingalkoxide compound, an aluminum-containing amine compound, or a compoundmodified therefrom.
 11. The method of claim 1, wherein the thirdmaterial comprises at least one of H₂O, O₂, O₂ plasma, N₂O, N₂O plasma,O₃, H₂O plasma, NH₃, NH₃ plasma and N₂ plasma.
 12. The method of claim1, wherein the deposition film comprises at least one of Si, Ge,Si_(x)Ge_(1−x)(0<x<0.5), boron-doped Si, phosphorus-doped Si,carbon-doped silicon, an oxide semiconductor, a nitride semiconductor,ZnO, NiO, CeO, EuO, AlN, GaN and InN.
 13. The method of claim 1, whereinthe first material layer comprises at least one of a silicon-containinginorganic compound, a germanium-containing inorganic compound, a carboncompound.
 14. The method of claim 13, wherein the first material layercomprises at least one of a silicon hydride compound, a silicon chloridecompound, a germanium hydride compound and a germanium chloridecompound.
 15. The method of claim 1, wherein the first material layercomprises at least one of SiH₄, SiCl₄, Si₂H₆, Si₂Cl₆, SiH₂Cl₂, Si₃H₈,GeH₄, GeCl₄, Ge₂H₆, Ge₂Cl₆, GeH₂Cl₂ and Ge₃H₈.
 16. The method of claim1, wherein the first material comprises at least one of CH₄, C₂H₆, C₃H₈,(CH₃)SiH₃, (CH₃)GeH₃, (C₂H₅)SiH₃ and (C₂H₅)GeH₃.
 17. The method of claim1, wherein the deposition film comprises an oxide semiconductor, and thefirst material layer comprises at least one of an alkyl compound, analkoxide compound, a nitride semiconductor, a compound modified from;and the first material layer comprises at least one of dimethylaluminumhydride, trimethylaluminum, triethylaluminum, trimethylgallium,triethylgallium, trimethylindium, triethylindium and a compound modifiedtherefrom.
 18. The method of claim 1, wherein the deposition filmcomprises a nitride semiconductor, and the first material comprises atleast one of dimethylethylaminealuminum, dimethylaminobutylaluminum anda compound modified therefrom.
 19. The method of claim 1, wherein thedeposition film comprises Si, Ge or Si_(x)Ge_(1−x)(0<x<0.5), the thirdmaterial comprises hydrogen or hydrogen radical, and forming thedeposition film comprises pyrolyzing the first material layer.
 20. Themethod of claim 1, wherein the third material comprises at least one ofnitrogen radical, NH₃, NH₃ plasma and N₂ plasma.
 21. The method of claim1, wherein forming the deposition film comprises exposing the substrateto remote plasma, microwave, electron cyclotron resonance plasma or UV(Ultraviolet) light.
 22. The method of claim 1, wherein the depositionfilm comprises metal, metal compound, or a metal-silicon compound. 23.The method of claim 1, wherein the deposition film comprises at leastone of Al, Ti, Ta, W, Cu, TiN, TaN, WN, GeSbTe, CuInGaSe, NiSi, CoSi andTiSi.
 24. The method of claim 1, wherein the first material comprises atleast one of an inorganic metal compound, an alkyl compound and acompound modified therefrom.
 25. The method of claim 1, wherein thefirst material comprises at least one of AlCl₃, TiCl₄, TaCl₅ and WF₆.26. The method of claim 1, wherein the first material comprises at leastone of trimethylaluminum, triethylaluminum and dimethylaluminum hydride.27. The method of claim 1, wherein the second material reacts with thefirst material to form a volatile material.
 28. The method of claim 31,wherein the second material comprises at least one of hydrogen,chlorine, fluorine, hydrogen radical, chlorine radical and fluorineradical.
 29. The method of claim 31, wherein the second materialcomprises at least one of HCl, BCl₃, ClF₃ and NF₃.
 30. The method ofclaim 31, wherein removing the first material layer comprises exposingthe substrate to remote plasma, a radical generation apparatus,microwave, electron cyclotron resonance plasma or UV (Ultraviolet)light.
 31. The method of claim 34, wherein removing the first materiallayer comprises adjusting an incident angle of UV (Ultraviolet) light tothe substrate such that UV light is not radiated on the surface of theone or more recesses.
 32. The method of claim 1, further comprisingforming OH bonds on the surface of the substrate before forming thefirst material layer by exposing the substrate to H₂O plasma, remote H₂Oplasma or (OH)* radical.
 33. The method of claim 1, wherein forming thefirst material layer, removing the first material layer and forming thedeposition film are repeated at least two times, respectively.
 34. Themethod of claim 1, further comprising forming an additional depositionfilm over the entire surface of the substrate.
 35. A method ofmanufacturing a device comprising the method of forming a substratestructure, comprising: forming a first material layer on a substrate,one or more recesses formed on the substrate; removing the firstmaterial layer from the substrate other than surfaces of the one or morerecesses using a second material that reacts with the first materiallayer; and forming a deposition film from the first material layer usinga third material that reacts with the first material layer.
 36. A methodof forming a substrate structure, comprising: forming a deposition filmon a substrate having one or more recesses; and removing the depositionfilm from the substrate other than for surfaces of the one or morerecesses using a first material that reacts with the deposition film.37. The method of claim 36, wherein removing the deposition filmcomprises controlling duration for exposing the substrate to the firstmaterial such that the surfaces of the one or more recesses are notexposed to the first material.
 38. The method of claim 36, furthercomprising exposing the substrate to a purge gas and pumping out thepurge gas responsive to forming the deposition film or removing thedeposition film.
 39. The method of claim 36, wherein forming thedeposition film comprises exposing the substrate to a source precursorand a reaction precursor.
 40. The method of claim 39, wherein the sourceprecursor comprises silicon or aluminum.
 41. The method of claim 40,wherein the source precursor is a silicon-containing inorganic compound,a silicon hydride compound or a silicon chloride compound.
 42. Themethod of claim 41, wherein the source precursor comprises at least oneof SiH₄, SiCl₄, Si₂H₆, Si₂Cl₆, SiH₂Cl₂ and Si₃H₈.
 43. The method ofclaim 41, wherein the source precursor is at least one of asilicon-containing organic compound or an aluminum-containing organiccompound.
 44. The method of claim 43, wherein the source precursor is analkyl compound having an Si—H bond, an alkoxide compound having an Si-Hbond, a siloxane compound having an Si—H bond, a silicon-containingamine compound, an aluminum-containing alkyl compound, analuminum-containing alkoxide compound, an aluminum-containing aminecompound, or a compound modified therefrom.
 45. The method of claim 36,wherein the first material reacts with the deposition film to form avolatile material.
 46. The method of claim 45, wherein the firstmaterial comprises at least one of hydrogen, chlorine, fluorine,hydrogen radical, chlorine radical and fluorine radical.
 47. The methodof claim 45, wherein the first material comprises at least one of HCl,BCl₃, ClF₃ and NF₃.
 48. The method of claim 36, wherein removing thedeposition film comprises exposing the substrate to remote plasma, aradical generation apparatus, microwave, electron cyclotron resonanceplasma or UV (Ultraviolet) light.
 49. The method of claim 48, whereinremoving the deposition film comprises adjusting an incident angle of UV(Ultraviolet) light to the substrate such that the UV light is notradiated in the one or more recesses.
 50. The method of claim 36,wherein the deposition film comprises an atomic layer of silicon,aluminum or titanium.
 51. The method of claim 36, further comprisingforming a modified film by reaction of the deposition film and a secondmaterial.
 52. The method of claim 36, wherein the second materialcomprises at least one of H₂O, O₂, O₂ plasma, N₂O, N₂O plasma, O₃, H₂Oplasma, NH₃, NH₃ plasma and N₂ plasma.
 53. The method of claim 36,wherein the modified film comprises at least one of SiN, SiO₂, AlN,Al₂O₃, TiN and TiO₂.
 54. The method of claim 36, further comprisingforming OH bonds on the surface of the substrate before forming thedeposition film.
 55. The method of claim 36, wherein forming OH bondscomprises exposing the substrate to H₂O plasma, remote H₂O plasma or(OH)* radical.
 56. The method of claim 36, wherein forming thedeposition film and removing the deposition film are repeated at leasttwo times, respectively.